Rapid identification of the quality decoction pieces by partial least squares ‐based pattern recognition: grade classification of the decoction pieces of Saposhnikovia divaricata

Herbal medicines are commonly used in many countries after they undergo processing. Quality decoction pieces are a guarantee of the efficacy and safety of the herbal medical products. Here, a strategy based on chemical analysis combined with chemometric techniques was proposed for the classification and prediction of the different grades of the decoction pieces. Considering the necessity for a shared and simple method for the grade classification for the public, in this paper, the characterization of the chemical constituents was determined by utilizing high‐performance liquid chromatography (HPLC)/diode array detection. HPLC was first established for the characterization of the chemical constituents of the different grade decoction pieces. Furthermore, a simultaneous quantification of several of the marker compounds in these decoction pieces was obtained. Finally, a partial least squares‐based pattern recognition method was utilized to obtain a predictive model for the grade classification of the decoction pieces. Saposhnikovia divaricata (Turcz.) Schischk was used as a case study. The partial least squares ‐based pattern recognition for the grade classification of the decoction pieces of S. divaricata demonstrated good sensitivity, specificity and prediction performance, which may efficiently validate the identification results of appearance assessment. The proposed strategy is expected to provide a new insight for the grade classification and quality control of the decoction pieces. Copyright © 2016 John Wiley & Sons, Ltd.     

Surface-enhanced Raman scattering spectroscopic analysis of Saposhnikovia divaricata decoction

ABSTRACT

Surface-enhanced Raman scattering spectroscopy was employed to analyze the biochemical composition of the Saposhnikovia divaricata decoction, which is a common traditional Chinese medicine. No reliable Raman peak was observed in traditional Raman spectra of Saposhnikovia divaricata decoction. However, 12 main Raman peaks (534, 616, 648, 685, 730, 781, 850, 958, 1242, 1319, 1460, and 1571 cm^?1) were observed in the surface-enhanced Raman scattering spectroscopy spectra from the mixture of silver colloids with Saposhnikovia divaricata decoction as a result of the silver colloid enhanced effects on the Raman scattering of Saposhnikovia divaricata decoction. The results demonstrated that the surface-enhanced Raman scattering spectroscopy may provide a new kind of non-destructive, accurate, direct, and fast detecting method for the Saposhnikovia divaricata decoction or other traditional Chinese medicine in the form of decoction.     

In vivo metabolism study of rhubarb decoction in rat using high-performance liquid chromatography with UV photodiode-array and mass-spectrometric detection: a strategy for systematic analysis of metabolites from traditional Chinese medicines in biological samples

High-performance liquid chromatography with diode-array detection (HPLC-DAD) and tandem mass spectrometry (HPLC-MS/MS) was used for separation and identification of metabolites in rat urine, bile and plasma after oral administration of rhubarb decoction. Based on the proposed strategy, 91 of the 113 potential metabolites were tentatively identified or characterized. Besides anthraquinones metabolites, gallic acid, (-)-epicatechin and (+)-catechin metabolites were also detected and characterized in these biological samples. Our results indicated that glucuronidation and sulfation were the main metabolic pathways of anthraquinones, while methylation, glucuronidation and sulfation were the main metabolic pathways of gallic acid, (-)-epicatechin and (+)-catechin. Phase I reactions (e.g., hydroxylation and reduction) played a relatively minor role compared to phase II reactions in metabolism of phenolic compounds of rhubarb decoction. The identification and structure elucidation of these metabolites provided essential data for further pharmacological and clinical studies of rhubarb and related preparations. Moreover, the results of the present investigations clearly indicated the relevance and usefulness of the combination of chromatographic, spectrophotometric, and mass-spectrometric analysis to detect and identify metabolites.     

Roles of paeoniflorin and senkyunolide I in SiWu decoction on antiplatelet and anticoagulation activities

Traditional Chinese medicine (TCM) is a complex system, which consists of numerous compounds with related mechanisms to maximize therapeutic efficacy with minimal adverse effects. Some new methods disclosing the contribution of these constituents as well as their relationship in the formula are necessary for elucidating the bio‐active constituents and the working mechanisms of TCM. In this study, depletion of target components using preparative HPLC followed by antiplatelet and anticoagulation activities evaluation was first applied to investigate the roles of paeoniflorin and senkyunolide I in a well‐known formula, SiWu decoction. The results showed that both paeoniflorin and senkyunolide I not only directly brought about some bio‐activities, but also indirectly made the contribution to the total bio‐activity reflection of SiWu decoction, especially the latter should deserve to be drawn attention to the research of complicated bio‐active constituents of TCM or its formula. So, the significant and effective approach will be very useful for the elucidation of the contribution of each different chemical constituent to the bio‐activity of a TCM formula. Furthermore, this study demonstrated the potential utilization of preparative HPLC in the research of TCM.     

Ayurvedic preparation of Zingiber officinale Roscoe: effects on cardiac and on smooth muscle parameters

The rhizome of the Zingiber officinale Roscoe, a biennial herb growing in South Asia, is commonly known as ginger. Ginger is used in clinical disorders, such as constipation, dyspepsia, diarrhoea, nausea and vomiting and its use is also recommended by the traditional medicine for cardiopathy, high blood pressure, palpitations and as a vasodilator to improve the circulation. The decoction of ginger rhizome is widely used in Ayurvedic medicine. In this papery by high-performance liquid chromatography, we have seen that its main phytomarkers were 6-gingerol, 8-gingerol and 6-shogaol and we report the effects of the decoction of ginger rhizome on cardiovascular parameters and on vascular and intestinal smooth muscle. In our experimental models, the decoction of ginger shows weak negative inotropic and chronotropic intrinsic activities but a significant intrinsic activity on smooth muscle with a potency on ileum is greater than on aorta: EC₅₀ = 0.66 mg/mL versus EC₅₀ = 1.45 mg/mL.     

Simultaneous determination of baicalin,baicalein, wogonoside,wogonin, scutellarin,berberine, coptisine,ginsenoside Rb1 and ginsenoside Re of Banxia xiexin decoction in rat plasma by LC–MS/MS and its application to a pharmacokinetic study

A rapid and high‐sensitivity liquid chromatography/tandem mass spectrometry (LC/MS/MS) method was developed for simultaneous determination of nine active constituents (baicalin, baicalein, wogonoside, wogonin, scutellarin, berberine, coptisine, ginsenoside Rb1 and ginsenoside Re) in rat plasma after oral administration of Banxia xiexin decoction (BXD). Biological samples were processed wtih acetone–ethyl acetate (4:1, v/v). The mobile phase consisted of methanol and water (containing 0.1% formic acid) with gradient elution at a flow rate of 0.3 mL/min. Detection was performed on a triple quadrupole mass spectrometer using positive ion and negative ESI in the multiple reaction monitoring mode. The calibration curves for all analytes had good linearity (r > 0.9933). The mean recovery of all the nine active ingredients was >75.2%, and the intra‐ and inter‐day precisions were within 12.0%; the accuracy was between 87.4 and 110.4%. This method was successfully applied to a pharmacokinetic study after administration of BXD. The results of the pharmacokinetic study might be helpful for BXD reasonable clinical application and further studies on mechanism.     

Effects of Tao‐Hong‐Si‐Wu decoction on acute blood stasis in rats based on a LC‐Q/TOF‐MS metabolomics and network approach

A novel approach using metabolomics coupled with a metabolic network was used to investigate the effects of Tao‐Hong‐Si‐Wu decoction (THSWD) on the rat model of acute blood stasis syndrome. Acute blood stasis syndrome was induced by placing the rats in ice‐cold water following two injections with epinephrine. The hemorheological indicators [whole blood viscosity (WBV) and plasma viscosity (PV)] and the blood coagulation indicators [thrombin time (TT), prothrombin time (PT), activated partial thromboplastin time (APTT) and fibrinogen (FIB)] were detected. The nonparametric univariate method and multivariate statistical analysis were performed for determining the potential biomarkers. A correlation map was structured between biochemical indicators and hub metabolites to explain the effects mechanism of THSWD. After the administration of THSWD, the levels of WBV, PV, TT, APTT and FIB returned to levels observed in the control group. According to metabolomics coupled with metabolic network analysis, the intervention of THSWD in rats with acute blood stasis syndrome induced substantial and characteristic changes in their metabolic profiles. Fifteen metabolites were screened, which mainly involved 10 pathways and five hub metabolites, namely, l ‐glutamate, l ‐phenylalanine, N‐acylsphingosine, arachidonic acid and phosphatidate. The biochemical indicators and hub metabolites could be adjusted to close to normal levels by THSWD. Therefore, combining metabolomics and metabolic network helped to evaluate the effects of THSWD on acute blood stasis.     

Chemical interaction between Lilium brownii and Rhizoma Anemarrhenae,the herbal constituents of Baihe Zhimu decoction,by liquid chromatography coupled to hybrid triple quadrupole linear ion trap mass spectrometer

During the course of decoction, the components of herbal formula interact with each other, such that chemical extraction characteristics are altered. The crude drugs, Lilium brownii (Baihe) and Rhizoma Anemarrhenae (Zhimu), are the herbal constituents of Baihe Zhimu decoction, a traditional herbal formula. To investigate the chemical interaction between Baihe and Zhimu when decocting together, eight marker components in Baihe Zhimu decoction were simultaneously characterized and quantified in one run by a hybrid triple quadrupole linear ion trap mass spectrometer in the multiple reactions monitoring–information dependent acquisition–enhanced product ion mode. The results showed that Zhimu significantly suppressed the extraction of phenolic glycosides (the components from Baihe) when co‐decocting, and Baihe clearly suppressed the extraction of xanthones and steroidal saponins (the components from Zhimu). Overall, the presently developed method would be a preferred candidate for the investigation of the chemical interaction between herbal medicines.     

Qualitative and quantitative analysis of the chemical constituents in Mahuang‐Fuzi‐Xixin decoction based on high performance liquid chromatography combined with time‐of‐flight mass spectrometry and triple quadrupole mass spectrometers

High‐performance liquid chromatography coupled with time‐of‐flight mass spectrometry (HPLC‐TOF/MS) and high‐performance liquid chromatography–triple quadrupole mass spectrometry (HPLC‐QQQ/MS/MS) were utilized to clarify the chemical constituents of Mahuang‐Fuzi‐Xixin Decoction. There are 52 compounds, including alkaloids, amino acids and organic acids were identified or tentatively characterized by their characteristic high resolution mass data by HPLC‐QQQ/MS/MS. In the subsequent quantitative analysis, 10 constituents, including methyl ephedrine, aconine, songrine, fuziline, neoline, talatisamine, chasmanine, benzoylmesaconine, benzoylaconine and benzoylhypaconine were simultaneously determined by HPLC‐QQQ/MS/MS with multiple reaction monitoring mode. Satisfactory linearity was achieved with wide linear range and fine determination coefficient (r > 0.9992). The relative standard deviations (RSD) of inter‐ and intra‐day precisions were <3%. This method was also validated by repeatability, stability and recovery with RSD <3% respectively. A highly sensitive and efficient method was established for chemical constituents studying, including identification and quantification of Mahuang‐Fuzi‐Xixin decoction.     

Determination and pharmacokinetics of geniposidic acid in rat plasma after oral administration of Gardenia jasminoides fruit crude extract and Zhi‐zi‐chi decoction

A simple and efficient liquid chromatography–mass spectrometry method was developed and validated for the determination of geniposidic acid in rat plasma. After the addition of internal standard salidroside and acidification (0.1% formic acid, pH = 3.2), plasma samples were carried out by protein precipitation with acetonitrile and separated on a Kromasil C₁₈ column (150 × 4.6 mm, 5 µm) within a run time of 9.0 min. Analysis was performed in selected ion monitoring mode with a positive electrospray ionization interface. No endogenous interference was observed at retention times of the analytes because of the high specificity of selected ion monitoring mode. The linear range was 0.02–4.0 µg/mL and the lower limit of quantification was 0.02 µg/mL. The mean extraction recoveries of geniposidic acid and internal standard from rat plasma were all >88.0% and the matrix effects were within acceptance criteria (90–110%). The validated method was successfully applied to the pharmacokinetic study of geniposidic acid in rat plasma after oral administration of G. jasminoides fruit crude extract and Zhi‐zi‐chi decoction, respectively. Copyright © 2013 John Wiley & Sons, Ltd.